Unique battery with a multi-functional, physicochemically active membrane separator/electrolyte-electrode monolith and a method making the same

ABSTRACT

The invention relates to a unique battery having a physicochemically active membrane separator/electrolyte-electrode monolith and method of making the same. The Applicant&#39;s invented battery employs a physicochemically active membrane separator/electrolyte-electrode that acts as a separator, electrolyte, and electrode, within the same monolithic structure. The chemical composition, physical arrangement of molecules, and physical geometry of the pores play a role in the sequestration and conduction of ions. In one preferred embodiment, ions are transported via the ion-hoping mechanism where the oxygens of the Al 2 O 3  wall are available for positive ion coordination (i.e. Li + ). This active membrane-electrode composite can be adjusted to a desired level of ion conductivity by manipulating the chemical composition and structure of the pore wall to either increase or decrease ion conduction.

RELATION TO PREVIOUS PATENT APPLICATIONS

The present application is a continuation in part of, and claimspriority to U.S. Non-Provisional patent application Ser. No. 11/690,413filed on Mar. 23, 2007, now U.S. Pat. No. 8,119,273, which claimspriority to U.S. Non-Provisional patent application Ser. No. 11/031,960filed on Jan. 7, 2005, now abandoned, which claims priority to U.S.Provisional Patent Application No. 60/535,122 filed on Jan. 7, 2004, byinstant inventors, all of which are hereby incorporated by reference intheir entireties.

U.S. GOVERNMENT RIGHTS

The United States Government has rights in this invention pursuant toContract No. W-31-109-ENG-38 between the U.S. Department of Energy andthe University of Chicago, representing Argonne National Laboratory.

TECHNICAL FIELD

The invention relates to a unique battery having an activatedmembrane/electrode monolith and method of making the same. Morespecifically one preferred embodiment of the present invention is amonolithic system employing a novel physicochemically active membraneseparator/electrolyte/electrode (PAMSEE) monolith, which acts as aseparator and electrolyte, and an integrated electrode.

BACKGROUND OF THE INVENTION

Increased use of consumer electronics such as cellular telephones,laptop computers and other portable devices, and the development of newtechnologies like electric vehicles (EV) has increased the demand forcompact, durable, high energy capacity batteries. This demand iscurrently being filled by a variety of battery technologies includingtraditional lithium-ion batteries. The flammable liquid electrolytecontained in lithium-ion batteries poses a safety hazard and must besecurely contained by the battery package. However, the metal andplastic packaging of traditional batteries makes them heavy, thick,prone to leakage and difficult to manufacture. New generations ofsolid-state batteries are emerging that allow the fabrication ofconsumer batteries in a wide variety of shapes and sizes that arethinner, safer and more environmentally friendly. However, state of theart, solid-state batteries have several shortcomings includingrelatively low values of ion conductivity.

Lithium polymer electrolytes have received considerable interest for usein solid-state batteries. These electrolyte systems are complexmaterials composed of amorphous and crystalline phases. It has beenknown since 1983 that the ion motion in polymer electrolytes occurspredominantly in the amorphous phase. Accordingly, the conventionalapproach to improving ionic conductivity has been to investigateconditions that either decrease the degree of crystallinity or increasethe segmental motion of the polymer matrix. However, despite significantimprovements, modern lithium-ion batteries employing polymerelectrolytes are limited by lithium ion conductivities of order 10⁻⁶ Scm⁻¹ at ambient temperatures. This level of conductivity is notsufficient for many consumer battery applications.

The 10⁻⁶ S cm⁻¹ conductivity ceiling was overcome by true solid-statebatteries developed by Duracell in the 1970s which used pressed aluminumoxide (Al₂O₃) powder and Li salt (LiI) as the electrolyte material. See,U.S. Pat. No. 4,397,924 issued to Rea on Aug. 9, 1983 (Rea '924). Thesolid alumina electrolyte provided two orders of magnitude greaterconductivity than polymer electrolytes. In one view, the lithium ionstravel across the surfaces of alumina particles by hoping from oxideoxygen to oxide oxygen on the amorphous surface. (Kluger K, Lohrengel M,Berichte Der Bunsen-Gesellschaft-Physical Chemistry Chemical Physics, 95(11): 1458-1461 NOV (1991)). However, this ion conduction only occurswhen sufficient contact between adjacent alumina particles is bothcreated and maintained. The Rea '924 patent overcame the first part ofthe contact problem by severely compressing the components atcompressive strengths of order 100,000 psi. The result is a very densesolid-state electrolyte. However, overtime the ionic conductivity of theelectrolyte decreased perhaps because the contact between particlesdegraded. This was especially expected when the electrolyte wassubjected to shock or other mechanical trauma. Because Rea relied onphysical compression to create contact between alumina particles, verysmall changes in the contact between the alumina particles could have aprofoundly negative effect on the ion conduction of the material. Infact, it appears that this technology was virtually abandoned because ofthis limitation.

Recently porous anodized aluminum oxide (AAO) membranes were consideredfor use as battery materials by other researchers, however, themechanism for lithium-ion conductivity of the membrane itself hasneither been considered nor explored, nor has the modification andadjustment of the membrane. For example, U.S. Pat. No. 6,586,133 issuedto Teeters et al., on Jul. 1, 2003 (Teeters '133) teaches a nano-batteryor micro-battery produced by a process comprising: providing a membranewith a plurality of pores having diameters of 1 nm to 10 μm, filing saidmembrane with an electrolyte; and capping each filled pore with anelectrode from about 1 nm to about 10 μm in diameter in communicationwith said electrolyte to form individual nano-batteries ormicro-batteries. While Teeters '133 suggests the use of porous aluminumoxide membranes, it teaches the membranes solely as an innocuous,inactive, “jacket” for containing or housing nano or micro cells. TheTeeters patent is directed solely to the creation of nano- andmicro-size batteries and never teaches or even suggests using an activemembrane to enhance the ion conductivity of the electrolyte in asynergistic manner. For example, the preferred pore diameter range ofTeeters' system (up to 10 microns) is much too large for meaningful ionconductivity enhancement by the metal oxide membrane itself. Teetersteaches miniaturization of existing battery technology for the purposeof providing power to micro-scale machines. Furthermore, Teeters teachesthe use of AAO membranes with low pore densities and porosities whichare inadequate for producing effective active (highly conductive)membranes. Thus, the membrane pores of Teeters function as simplecompartments for containing a stack of anode, electrolyte, and cathodematerials to form a cell. Teeters also teaches that the anode andcathode material of the preferred embodiment are contained inside thepore of the AAO membrane. Teeters invention, can be fabricated equallywell by employing a variety of materials having pores. The principle ofTeeters is the miniturization of a battery cell using AAO as amicro-container, not as a material for enhancing the performance of thebattery itself.

Mozalev, et al. teach a porous alumina membrane as the separator formacrobatteries. See, A. Mozalev, S. Magaino, H. Imai, ElectrochimicaActa, 46, 2825 (2001). Their work suggested that alumina membranesmechanically suppress Li dendrite formation, thereby improving cyclingefficiencies. However, they have not suggested or discussed thelithium-coordinating role that modified aluminum oxide membrane wallscan play. The object of the Mozalev invention is to mitigate formationof dendrites by use of a hard material for a battery separator. Anyhard, porous, material will serve the object of Mozalev's invention.

U.S. Pat. No. 6,705,152 issued to Routkevitch et al., discloses a typenano-structured ceramic platform for gas sensors. Routkevitch's sensorscomprise micro-machined anodic aluminum oxide films having high densitynano-scale pores, sensing materials deposited inside the self-organizednetwork of nano-pores and at least one electrode deposited on the AAO.The gas permeable electrodes are deposited upon the AAO so to provideelectronic conductivity without closing the pores to outside gases, soto enable gas sensing. The object of Routkevitch's invention is to makenano- or micro-sensing devices for detecting various substances at tracelevels. Routkevitch teaches sensor devices that are open systems. Thus,the sensing materials deposited inside the network of nano-pores and theelectrodes are continuously exposed to gas and liquid molecules from theambient environment. A sensor device with blocked, clogged, or coverednano-pores is a closed system, and is not capable of performing thefunctions of sensing.

A major breakthrough in the room-temperature conductivity of lithiumpolymer electrolytes would significantly impact the rechargeableconsumer battery market, as well as the emerging electric vehicle (EV)arena. Despite more than 20 years of active industrial and academicinvestigation, the current level of conductivity for lithium polymerelectrolytes is not sufficient for many battery applications andsuggests that a radical new approach based on a better understanding ofion transport is required. No prior art system provides a monolithicmembrane which acts as a separator, electrolyte and electrodesimultaneously.

SUMMARY OF INVENTION

The present invention relates to a unique battery system employing anovel multi-functional monolith that acts as a separator, electrolyte,and electrode (i.e. PAMSEE).

One embodiment of the invention relates a specialized battery producedby a process comprising:

a monolithic based membrane/electrode having a first and second side,the first side being a metal or metal alloy (electrode section orcomponent) and the second side being an anodized metal oxide or oxidizedmetal alloy (membrane section or component), the m/e having a pluralityof pores running the thickness of the second side of the basemembrane/electrode terminating into the first side of the membrane, andwherein the base membrane/electrode pores have an inner wall; whereinthe first and second sides each have an outer face, and wherein thepores have diameters ranging from about 2 nm to about 150 nm.

wherein the inner pore walls of the m/e are coated with a defined porecoating selected from the group consisting of: salts, anions, cations,ion conducting polymers compounds and combinations thereof, activatedthe membrane/electrode (i.e. transforming the m/e into a firstphysicochemically active membrane separator/electrolyte/electrode(PAMSEE) monolith);

a first outer electrode attached or deposited on the face of the PAMSEEsecond side, wherein the first side of the PAMSEE acts as the secondelectrode, wherein the first outer electrode covers the pores on thesecond side's face to form a first seal, and wherein the electrodesseal-off the pores from the ambient environment.

While prior art references teach the use of certain specializedmaterials like AAO as part of an electrolyte (Rea '924) and as a nano ormicro-container for the creation of nano and macro batteries (Teeters'133), the prior art fails to teach or even suggest the use of welldefined, physically and chemically active membrane separator,electrolyte, electrode PAMSEE (wherein the pores of the membrane sectionare coated with at least one ionic species) capable of ion-coordinationand ion conduction of large quantities of charge (>1 mC), which act asboth a separator, electrode and electrolyte. Unlike the innocuousmembrane disclosed in Teeters '133, the membrane section of the novelPAMSEE is designed to transport large quantities of ions without theaddition of an electrolyte to the pore. Thus, a key component inTeeter's invention, the electrolyte, is replaced by an activatedmembrane channel in the present invention.

The Applicants' invented battery employs a PAMSEE that acts as aseparator, electrolyte, and electrode, within the same monolithicstructure. In one preferred embodiment, ions in the AAO pores of themembrane section of the PAMSEE are transported via an ion-hopingmechanism where the oxygens of the Al₂O₃ wall are available for positiveion coordination (i.e. Li⁺). This activated membrane/electrode can beadjusted to a desired level of ion conductivity by manipulating thechemical composition and structure of the pore wall to either increaseor decrease ion conduction. Physical aspects of the active membranesection (i.e. pore size, porosity and tortuosity) can also be varied tocontrol conductivity. This adjustability allows one to create customizedmembranes and batteries specifically tailored for a particularapplication. It may be preferable that the membrane be unidirectionalfor certain applications. The AAO portion (i.e. membrane section) ofApplicants' invention is more fully described in U.S. Provisional PatentApplication No. 60/535,122 filed on Jan. 7, 2004, and U.S.Non-Provisional patent application Ser. No. 11/031,960 filed on Jan. 7,2005, by instant inventors, both of which are hereby incorporated byreference in their entireties.

A salient aspect of at least one embodiment of the present inventionrelates to an electrochemical cell having a multi-functionalmembrane/electrode composite, the membrane section of themembrane/electrode having physicochemically functionalized ion channelscapable of adjustable ionic interaction, wherein the pores of saidmembrane section are modified by physical, chemical, or electrochemicalmeans to impart atomic coordination sites for positive ions or negativeions transforming the membrane/electrode into a PAMSEE.

An advantage of at least one embodiment of the membrane/electrode of thebattery is the ability to tailor the ion-conductivity of the membranesection (i.e. AAO portion) for specific uses. For example,ion-conductivity could be maximized for applications requiring fastresponses and/or large amount of energy per unit time (i.e. EVacceleration) while ion conductivity could be lowered for less strenuousapplications where high ion conductivity is not needed and/or ifavailable would pose a safety hazard.

A salient aspect of at least one embodiment of the present invention ischanging the physical characteristics of the membrane section of themembrane/electrode and its pores (i.e. pore diameter, porosity,tortuosity etc.) in order to tailor the functionality of theseparator/electrolyte membrane component.

Another embodiment of the present invention relates to a battery havinga PAMSEE in which the second side or face is coated with anion-conducting polymer creating a laminate-membrane that obviatesproblems associated with ion transport at the interface and polarization(i.e., the spatial depletion of ions in an electrolyte material suchthat a gradient in the ion concentration is formed, causing batteryfailure).

Another aspect of one embodiment of the invention relates to safetyfeatures of the PAMSEE which shut down the battery when criticaltemperatures are reached.

Yet another aspect of one embodiment of the invention relates to asynergistic membrane section of the PAMSEE component in which the wallsof the membrane pores are coated with ions and a polymer material likepolyethylene oxide and wherein the nanochannels of the AAO portion ofthe PAMSEE are preferably oriented normal to the electrodes, so as toprovide the shortest path between them. Thus, the pore walls of thissynergistic membrane section can act as a superhighway for maximizingion conduction, allowing ions to travel via the hoping mechanism of theAAO portion of the membrane/electrode composite, via segmental motionvia the polymer, via both mechanisms, or by a superposition mechanism.

An advantage of the present invention is a monolithic, multi-functionalactive membrane/electrode composite which acts a separator, electrolyteand electrode simultaneously.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A—is a side cross-sectional view of one embodiment of the basemembrane-electrode composite of the present invention.

FIG. 1B—is a side cross-sectional view of one embodiment of themonolithic separator/electrolyte membrane-electrode composite of thepresent invention.

FIG. 1C—is a side cross-sectional view of one embodiment of the inventedbattery incorporating a monolithic separator/electrolyte membrane and asecond electrode.

FIG. 2—is a top view of the second side of theseparator/electrolyte-electrode membrane showing the hexagonal porearrangement found in a preferred anodized aluminum oxide portion of themembrane.

FIG. 3—is a graph of voltage plotted on the ordinate and time plotted onthe abscissa representing the discharge curve of a cell comprised of analuminum disk cathode, a porous monolith membrane of anodized aluminumoxide having the interior surfaces of the pores coated with a polymerelectrolyte and functioning as a separator/electrolyte, and a lithiummetal film anode.

FIG. 4—depicts a ⁷Li MAS NMR spectrum of a LiI-coated AAO membrane(bottom) and LiI-coated nanoparticles from a separate source of alumina(top). The pore walls of the AAO membrane interact with LiI to producehighly mobile Li⁺ ions. The LiI/AAO system shows that approximately 50%of lithium is ionic and highly mobile; the remainder of lithium is lessmobile in LiI crystals. This spectrum shows that the walls have beencoated with LiI and the walls have activated the lithium ions forconduction.

FIG. 5—is a FTIR spectrum of a poly(ethylene oxide)—and poly(ethyleneglycol)-coated AAO membrane. The absorbance peak in the region 2800-2900cm⁻¹ confirms a coating of poly(ethylene glycol) or other polyethers onthe pore walls of the AAO membrane. The broad absorbance peak centeredbetween 3400 and 3500 cm⁻¹ indicates that surface hydroxides and watermolecules are also on the pore walls.

FIG. 6—illustrates one embodiment of the invented battery system having:a MnO₂ cathode and a monolithic separator/electrolyte membrane-aluminumanode composite.

FIG. 7—illustrates yet another embodiment of the invented systemcomprising: a lithium anode and a monolithic separator/electrolytemembrane-aluminum cathode composite.

FIG. 8—illustrates yet another embodiment of the invented systemcomprising a novel back-to-back double-cell battery employing amonolithic dual separator/electrolyte membrane-aluminum back-to-backelectrode.

FIG. 9A—is a side cross-sectional view of an alternate double-sidedembodiment of the monolithic dual separator membrane-aluminum electrodeof the present invention.

FIG. 9B—is a side cross-sectional view of an alternated double-sidedembodiment of the monolithic dual separator/electrolytemembrane-aluminum electrode of the present invention.

FIG. 9C—is a side cross-sectional view of an alternate double-sidedembodiment of the invented battery incorporating a monolithic dualseparator/electrolyte membrane-aluminum electrode and top and bottomelectrodes.

DETAILED DESCRIPTION OF THE EMBODIMENTS

FIG. 1C illustrates one preferred embodiment of the inventioncomprising:

a monolithic physicochemically active membraneseparator/electrolyte/electrode (PAMSEE) monolith 11 having a first 1and second side 2 (each side having an outer face 4 and 5 see, FIG. 1A),the first side 1 (electrode section) being a metal (or metal alloy) andthe second side 2 (membrane section) being an anodized metal oxide (oroxidized metal alloy), the PAMSEE having a plurality of pores 3 runningthe thickness of the second side terminating into the first side 1 andwherein the pores 3 have an inner wall covered with a defined coating 6;wherein the defined pore coating 6 is selected from the group consistingof: salts, anions, cations, ion conducting polymers compounds andcombinations thereof;

a first outer electrode 7 attached or deposited on the second side'sface wherein the first side 1 acts as the second electrode, wherein thefirst outer electrode 7 covers the pores on the second side's face toform a first seal, wherein the pores 3 have diameters ranging from about2 nm to about 150 nm and wherein the electrodes (1 & 7) seal-off thepores 3 of the membrane from the ambient environment.

The PAMSEE monolith acts as a separator/electrolyte as well as anelectrode. Details of the PAMSEE monolith are explained in detail below.In one preferred embodiment the PAMSEE monolith is created by coatingthe membrane pore walls 8 of a base membrane/electrode (FIG. 1A),creating a PAMSEE monolith having coated membrane pores 6 (FIG. 1B).Details of coating the pore walls are described herein. The PAMSEEmonolith is then combined with an additional electrode to create acomplete electrochemical cell (FIG. 1C).

Unique Separator/Electrolyte Membrane-Electrode

FIG. 1A illustrates one embodiment of a monolithic basemembrane/electrode having a first side 1 and second side 2, the firstside 1 being a metal (or metal alloy) and the second side 2 being ananodized metal oxide (or oxidized metal alloy), the basemembrane/electrode having a plurality of pores 3 running the thicknessof the second side 2 terminating into the metal of the second side (themetal of the second side acting as an electrode), and wherein the basemembrane/electrode pores have an inner wall 8. The first side has anouter face 4. The second side has an outer face 5 as well.

The inner pore walls of the membrane/electrode 8 are coated with adefined pore coating 6, (see, FIG. 1B), wherein the defined pore coating6 is selected from the group consisting of: salts, anions, cations, ionconducting polymers compounds and combinations thereof, producing anovel physicochemically active membrane separator/electrolyte-electrode(PAMSEE) monolith 10.

A salient feature of the invented electrochemical cell is theinteraction of the channel walls of the PAMSEE with ions and compoundsthat have varying degrees of activity with ions. The monolithicmembrane/electrode is preferably made by anodizing a metal (or metalalloy) to create a monolithic structure having a solid metal (or metalalloy) side and an anodized metal oxide (or metal alloy oxide) side.More preferably the membrane/electrode is made from aluminum creating astructure in which one side is solid aluminum and the other is porousanodized aluminum oxide.

Suitable metal oxides include but are not limited to amorphous titaniumoxide, titanium dioxide, di-titanium trioxide, AAO (anodized aluminumoxide), amorphous aluminum oxide, di-aluminum trioxide, alumina,crystalline alpha aluminum oxide, crystalline beta aluminum oxide,crystalline gamma aluminum oxide, magnesium oxide, silicone oxide,vanadium oxide, zirconium oxide, germanium oxide, tin oxide, galliumoxide, indium oxide, iron oxide, chromium oxide, molybdenum oxide,nickel oxide, copper oxide, zinc oxide and combination thereof. Variousmetal alloy-oxides could also be used. Anodized aluminum oxide, “AAO”,is a preferred metal oxide because of its adjustable physical porestructure and its good ion conducting ability.

The thickness of second side (anodized aluminum oxide side or membranesection) of the membrane/electrode 2 is a salient aspect of theinvention and can be varied according to desired results.Membrane/electrodes having membranes sections with thicknesses greaterthan 30 microns (i.e. about 30-50 microns) posses greater mechanicalstrength, but also have higher levels of resistance and are preferablewhen a robust membrane (and battery) is desired. Membranes sections of(about 10 nm-1000 nm) are better suited for high-power batteryapplications that require low resistance. Membranes/electrodes havingsecond sides of medium thickness (about 1 micron-30 microns) can be usedfor applications in between. Thin membrane sections are also useful insituations where the membrane is combined with a polymer, laminate orother substance that helps support the membrane (see, AAO-polymer hybridand AAO-laminate discussed below).

The ability to control the dimensions of the pores in AAO makes it anideal active membrane material. Controlling the physical and chemicalproperties of the membrane's pore walls allows the creation ofcustomized membranes tailored for specific uses. It is well known in theart that when anodized under certain conditions, the AAO pores form ahighly-ordered hexagonal arrangement of nano-channels perpendicular tothe metal electrode (anode) surface; and the pore diameter, pore length,pore spacing and pore-ordering are all adjustable by varying thecurrent, temperature, time, and choice of acidic electrolyte in whichthe membrane is grown (See, H. Masuda, M. Satoh, Jpn. J. Appl. Phys 35,126 (1996), see also, J. Li C. Papadopoulos, J. M. Xu, and M. Moskovits,App. Phys. Lett. 75, 367 (1999); Masuda and K. Fukuda, Science 268, 1466(1995); U.S. Pat. No. 6,139,713 issued to Masuda et al., and U.S. Pat.No. 6,705,152 issued to Routkevitch et al., of which are incorporated byreference in their entireties. The physical and chemical characteristicsof the pore walls are important variables in controlling ion-conduction.

FIG. 2 illustrates the typical hexagonal arrangement of the pores 3within the membrane portion of the membrane/electrode (second side).

Physical Modifications of the Membrane/Electrode

An important aspect of one embodiment of the invented PAMSEE monolith isthe surface area to volume (SA:V) ratio of the membrane pores. The poresof one preferred embodiment of the invented membrane have a surface areato volume ratio in the range 2×10⁷-2×10⁹ m⁻¹. A high SA:V ratiocorresponds to high levels of ion coordination and transport by a fastion-hoping mechanism on the membrane's pore walls. One achieves a highSA:V ratio by manipulating the diameter of the pores and the interporespacing. Of course, one can manipulate the SA:V ratio to tailor themembrane for different applications.

Decreasing the diameter of the nano-channels of the membrane section,increases the SA:V ratio and in turn increases the amount of ioncoordination by aluminum oxide and transport via its ion-hoping pathway.This allows control over the ion-coordinating ability of the AAO portionof the membrane/electrode composite monolith by manipulation of the poresize. The limited pore sizes of the membrane can also enhance theion-coordinating ability of polymers and/or other species present withinthe pores due to confinement-induced steric constraints. That is,limited pore-diameter size constrains polymer molecules, which causesthem to straighten out or adopt elongated chain conformations and thusbecome more efficient at transporting ions (unconstrained polymers wraparound ions to maximize coordination, and hinder rapid ion transport).

Although pore size can be adjusted, it is critical to the presentinvention that the pore diameter of the base membrane/electrodecomposite monolith is between about 2 nm-150 nm, to take advantage ofthe ion-hoping mechanism, and the advantageous effects of confinedion-conducting polymers. It is preferable to use pore size in the rangeof about 5-100 nm, and more preferably to use pore sizes in the range ofabout 5-50 nm.

Such a limited pore size range is in contrast to the prior art, whichteaches a wide range of pore diameters. Membrane/electrodes with porediameters greater than about 150 nm transport a majority of ionconduction via bulk electrolyte (if present) and not efficiently throughthe ion-hoping mechanism of AAO. Membranes/electrodes with porediameters less than 5 nm may be unpractical as they are difficult tomanufacture, can be difficult to chemically modify, and can be difficultto load with ions and polymer materials.

The porosity of the membrane/electrode composite monolith can also beused to tailor the ion conductivity. A suitable porosity range isbetween about 5-95%. The porosity depends on the intended use of themembrane device: low porosity (about 5-20%) for low-power batteryapplications; high porosity (about 20-65%) for high-power batteryapplications; highest porosity (about 65-95%) for very high powerbattery applications. See, also U.S. Pat. No. 6,627,344 issued to Kangon Sep. 20, 2003; U.S. Pat. No. 6,589,692 issued to Takami on Jul. 8,2003; and U.S. Pat. No. 5,290,414 issued to Marple on Mar. 1, 1994, allof which are hereby incorporated by reference in their entireties.

The tortousity of the pores of the membrane/electrode composite monolithis the distance the ions travel in traversing the pore structure(ratioed against) divided by the geometric width of the membranecomponent. A tortuosity of unity is generally considered the ideal valuefor high rates of ion conductivity as it represents a membrane componenthaving straight pores and thus the shortest distance between twoopposite faces, the minimum distance between the anode and cathode of abattery. However, a membrane-component having tortuosity values greaterthan 1 may be used to create a separator/electrolyte with varyingdegrees of conductivity. It may be possible to manipulate the tortuosityby growing the AAO in a magnetic field and varying the angle of themagnetic field relative to the direction the AAO is grown.

Once the base membrane/electrode component has been made, its pores canbe dilated by chemical etching, or contracted by processes such asatomic layer deposition and chemical vapor deposition. The first of thetwo pore-constricting processes can be used to fine tune the chemistryof the pore walls thereby changing the way in which the membranecomponent coordinates ions (i.e. Li⁺).

Chemical Modifications of the Membrane Component

The ion coordinating ability of the second side (membrane section) ofthe membrane/electrode composite monolith can be altered by manipulatingthe chemical structure of the matrix of the pore wall surface. The porewalls can be chemically modified by coating the walls with an organicsolution containing ions, an aqueous solution containing ions, anion-conductive polymer, or combinations thereof, which enhance or retardthe coordination and transport of ions. In addition, the charge of themetal oxide can be changed by treatment of the walls with acids orbases. Alternatively ion conducting salts or species can be melted orotherwise attached, absorbed or embedded in the pore wall surfaceactivated the membrane/electrode into a PAMSEE. The coating of the porewall has a thickness of less than about half the pore diameter of thebase membrane.

Salt Coating of AAO Membrane Pores

The invented membrane separator/electrolyte-electrode monolith can becreated by the addition of a variety of compounds and/or species to thepore walls, however, unlike prior art membranes; the presentmembrane/electrode composite monolith only requires the addition of asource of ions like a salt to become active. The activemembrane/electrode is the novel producing a first physicochemicallyactive membrane separator/electrolyte-electrode (PAMSEE) monolith.

Salt coatings can be added in a variety of ways including but notlimited to: soaking the pore walls with various salt-containingsolvents, spray-coating salt solutions, evaporative coating of volatilesalts, melting salts directly onto the pore walls and combinationsthereof. A variety of salts can be employed including numerous anhydroussalts.

When applying the salt using a solution, the pores are soaked with asolution containing the salt, and then the solvent is evaporated bytechniques well known in the art (i.e. heat) leaving a salt coating onthe walls of the pores.

In one embodiment the pore walls are treated with an organic solutionscontaining at least one ionic species. Suitable organic solutionsinclude, but are not limited to those, containing one or more of:methanol, formamide, propylene carbonate, ethylene carbonate,.gamma.-butyrolactone, 1,3-dioxolane, dimethoxyethane, dimethylcarbonate, methylethyl carbonate, diethyl carbonate, tetrahydrofuran,dimethyl sulfoxide and polyethylene glycol dimethyl ether; combined withat least one salt selected from the group (selected from): lithiumperchlorate (LiClO₄), lithium tetrafluoroborate (LiBF₄), lithiumhexafluorophosphate (LiPF₆), lithium trifluoromethanesulfonate(LiCF₃SO₃), lithium bistrifluoromethanesulfonyl amide (LiN(CF₃SO₂)₂),and lithium triflate.

In another embodiment the pores are treated with an aqueous solutioncontaining a salt or other ionic species. Suitable salts include but arenot limited to: ZnCl, AlCl₃, AlCl₃.6H₂O, Al(NO₃)₃, HCl, NH₄OH, H₂SO₄,NaOH, KOH, LiOH, CsOH, NaCl, KCL, CsCl, Al₂(SO₄)₃.

Alternately, the pore walls can be directly treated by melting the saltonto the surface of the pore wall. Preferred salts include but are notlimited to: lithium iodide, lithium bromide, lithium chloride, lithiumfluoride and combinations thereof.

Individual anions and cations (i.e. Li⁺ ions) can also be embedded intothe surface matrix of the pore walls. Embedding ions into the matrix canbe accomplished in a variety of ways including but not limited to thefollowing: The AAO portion of the membrane/electrode composite monolithis dried and evacuated to create open and clean pores. The evacuated AAOis exposed to metal alkoxides such as tetraethyl orthosilicate oraluminum isopropoxide or mixtures of metal alkoxides, which are insolution in dry organic solvents such as hexane. Reactions between themetal alkoxides and surface hydroxyl sites anchor the metal alkoxides tothe channel walls. The AAO portion of the membrane/electrode compositemonolith is further treated by exposure to water vapor and or hightemperatures to create a layered oxide surface. Bronsted acid sites,created via water and temperature treatments of the oxide layer, in adried and evacuated AAO membrane can be further exposed to gaseousammonia creating ammonium cation sites on the channel surface. Ammoniumcations can be ion-exchanged for other cations such as lithium, sodium,rubidium, and cesium to create an ion-specific surface in the AAOportion of the membrane-electrode composite monolith.

The chemical composition of the membrane component itself can bemodified to adjust the conductivity of the membrane. For example, mixedmetal oxides can be employed to get desired conductivity results.

AAO-Alumina Membrane Component

Yet in another preferred embodiment the pores are coated withnano-particles of alumina allowing ion-conduction via the ion-hopingmechanism by creating multiple parallel pathways for ion-conduction inthe AAO channels. The pores may also be coated with nano-particles ofother metal oxides for similar purposes.

AAO-Polymer Hybrid Membrane Component

In another preferred embodiment, the pores of the membrane/electrodecomposite monolith 3 are coated with a layer of ion-conductive polymer,creating a synergistic AAO-polymer membrane/electrode device. Suitablepolymers include but are not limited to: polyether, polyethylene oxide,polypropylene oxide, polyacrylonitrile, polyvinylidene fluoride,polyvinylidene chloride, polymethyl methacrylate, polymethyl acrylate,polyvinyl alcohol, polymethacrylonitrile, polyvinyl acetate,polyvinylpyrrolidone, polyethyleneimine, polybutadiene, polystyrene,polyisoprene, vinylidene fluoride-hexafluoropropylene copolymer,poly(ethylene oxide), poly(propylene oxide), polyethylene glycols,polypropylene glycols, propylene carbonate, ethylene carbonate, dioctylsebacate, diethyl phthalate, and derivatives of these polymers andcombinations thereof.

The polymer material can be deposited in a variety of ways including butnot limited to: adding a liquid solution of polymer in THF(tetrahydrofuran), or other volatile solvent, to the channels of themembrane drop-wise, and THF allowed to evaporate and disperse thepolymer.

Although the thickness of the polymer coating can be varied, thethickness is preferably less than or equal to about half the porediameter. Given that the diameters of pores are generally between 2-150nm, a suitable range of polymer thickness is generally between about1-149 nm, preferably between about 1-75 nm, dependent upon the diameterof the pores. The walls of the AAO-polymer hybrid membrane componentshould contain at least one ion conducting salt (or other ion conductingspecies). The salt can be coated on the walls of the AAO membranecomponent prior to the addition of the polymer or the salt can beincorporated within the polymer before the polymer is applied to thewalls of the pores.

The hybrid polymer-AAO membrane component allows ion conduction via twodifferent pathways: (1) the fast ion-hoping mechanism along the walls ofthe AAO pores and (2) a slower mechanism dependent on segmental motionthrough the polymer. It is believed that in certain embodiments, the twomechanisms work together in synergistic fashion to allow rates of ionconduction that exceed (or underseed) either of the mechanism workingalone. This synergistic membrane can be customized for a wide range ofapplications.

For applications requiring very high ion conductivity, cation conductioncan be designed almost exclusively via a polymer-assisted fast hoppingmechanism associated with alumina. This result is accomplished bylimiting the use of the polymer to a thin film. The desirable filmthickness is generally between about 1-20 nm thick, preferably 1-10 nmthick, most preferably between about 1-5 nm thick (along the surface ofthe AAO pore walls.) The pore walls of this synergistic membranecomponent act as a superhighway for ion-conduction, allowing ions totravel via the hoping mechanism on the AAO portion of themembrane-electrode composite monolith, via a segmental or modifiedsegmental motion (due to polymer-AAO interactions) or possibly by asynergism of ion displacement mechanisms. Applications with lower ionconduction requirements could be designed by increasing the amount ofpolymer present within the pores and thus the percentage of ioncoordination and transport via the bulk polymer segmental motionmechanism.

Laminated Membrane Component

In another preferred embodiment the outer face 5 (see FIG. 1A) of thesecond side 2 of the PAMSEE monolith (or first and second side inalternate double battery embodiment) is/are coated with a flation-conducting polymer film. This laminated PAMSEE monolith allows highion conduction through the AAO portion of the membrane-electrodecomposite monolith and allows enhanced contact between the outer face 5of the membrane component and electrode(s). A thin layer of soft polymerelectrolyte coating on the outer face 5 of the membrane componentcreates a bridging effect between the hard and uneven interfacialsurfaces of the electrode and the porous membrane component of thePAMSEE monolith that is beneficial for ion transport across the boundaryregion. In addition, the polymer electrolyte can permeate the porouselectrodes and contact interior regions of a porous electrode. This verythin polymer layer improves the conductivity across the membraneseparator/electrolyte-electrode interface, and obviates problemsassociated with polarization because ion diffusion over a thin polymerlayer rapidly equalizes ion concentration gradients. Furthermore, thehybrid PAMSEE monolith overcomes many problems associated with previousvery thin all-polymer membranes or thin polymer electrolyte films. Forexample, a mechanical puncture or breach of a polymer membrane separatorcan cause a dangerous short-circuit condition. The hard AAO membraneportion of the PAMSEE monolith would protect against mechanical puncturein the present embodiment. Thickness of the polymer coating ranges fromabout 1 nm to about 10 μm. The preferred thickness is determined by thesurface roughness of the electrode and AAO membrane portion of thePAMSEE monolith. Smoother surfaces might only require a coating of about1 μm or less. Rough surfaces require up to a about 10 μm thick (or eventhicker) coatings. This represents an improvement over existingsolid-state polymer electrolytes because in this application the polymerelectrolyte film can be made much thinner. Thin films mitigate thepolarization problem due to the sub-micron thickness of the films, adistance over which ion diffusion can rapidly equalize ion concentrationgradients.

Conventional polymer electrolyte films are limited by the polarizationeffect. It is desirable to make these films as thin as possible,preferably less than about 10 μm, which were unsafe in the prior art dueto short circuit safety concerns. However, thick films are required toprevent internal short circuit due to the roughness of the electrodesurface. In our application, a very thin film can be employed with outshort circuit hazards because of the hard AAO separator/electrolytemembrane located between the electrodes. The polymer can be a variety ofpolymers and can be deposited using a variety of techniques some ofwhich have been discussed earlier in the polymer-hybrid embodiment. Itshould be noted that the laminate is added to an active membrane, theactive membrane being described earlier (i.e. AAO-salt, AAO-polymerhybrid etc.).

Membrane Component w/Laminate Safety Fuse

Another embodiment incorporates a thermal safety fuse into the PAMSEEmonolith. For example, a thin layer of porous, non-ion conductingmaterial like polyethylene or polypropylene is deposited on the outerface 5 of the second side 2 of the PAMSEE monolith. The holes of theporous non-conducting material must allow access to the holes of thePAMSEE monolith so that ions can be conducted form cathode to anode in acell. The polymer top-coat is designed to melt at a battery temperaturewhere operation becomes unsafe, thus covering the active membrane holeswith a non-ionically conductive material, and disengaging the batterycircuit by inhibiting conduction. It should be noted that the laminateis added to an active membrane component, the active membrane componentbeing described earlier (i.e. AAO-salt, AAO-polymer hybrid etc.)Included below are examples of some of the various embodiments ofactivated AAO portion of the PAMSEE monolith of the present invention.

Membrane Example I Base Membrane/Electrode monolith w/Aluminum Electrode

IA.—Aluminum strips (6.0 cm×1.5 cm×0.15 mm) of 98% purity were immersedin 0.3 molal oxalic acid maintained at 276 K and anodized at 40 VDC,forming top and bottom transparent monolithic surface membranes having ametal (or metal alloy) interior and porous metal oxide (or metal alloyoxide) faces. The films were washed with deionized water, dried at 383 Kfor 15 minutes in air, and cooled under dry nitrogen. Removal of watercoating the pore walls was accomplished by heating the membranes to 330K under vacuum for two hours, or heating the membranes to 700 K underdry nitrogen.

IB.—Square pieces of aluminum foil (2.0 cm×2.0 cm×0.10 mm) of 99.999%purity were coated on one side with nail polished (to protect thecovered side from anodization) and dried and then immersed in 0.3 molaloxalic acid maintained at 276 K and anodized at 40 VDC for three daysuntil a transparent porous membrane was formed on the aluminumsubstrate. The films were washed with deionized water, dried at 383 Kfor 15 minutes in air, and cooled under dry nitrogen. Removal of watercoating the pore walls was accomplished by heating the membranes to 330K under vacuum for two hours, or heating the membranes to 700 K underdry nitrogen.

IC.—The AAO templates with pore sizes of about 20, 50, and 100 nm weregrown by potentiostatically anodizing aluminum plates (0.15 mm thick,99.9+% purity) in an aqueous solution of 14% H₂SO₄, 4%, and 2% oxalicacid respectively, and at a voltage of approximately 20V, 50V, and 100Vrespectively.

ID.—A device, called the single-sided anodizer was developed and isavailable from Argonne National Laboratory (Argonne, Ill.) to anodizeone side of a planar aluminum sample. This device was employed tosynthesize AAO in circular and other shaped areas on aluminum sheets anddisks. The aluminum sheet (of purity 99.999%) is actively cooled at thebottom face, and anodization is confined to the top face. Typically, ano-ring (diameter, 1.5 cm) is used to define a circular area that will beexposed to an aqueous 0.3 molal oxalic acid solution. A cylindricalcontainer is made to compresses the o-ring to form a seal between thealuminum surface, the o-ring, and the open base of the container. Thecontainer is filled with the acid solution (approximately 10 ml), whichis cooled to 275 K by contact with the cold aluminum. An aluminum metalstrip cathode electrode is positioned in the acid solution at the top ofthe container. A potential of 40V DC is applied between the cathode (−)and the aluminum sample to be anodized, anode (+). The current andtemperature are monitored by computer as the anodization processproceeds over a period of 1 week. The AAO sample is then removed andwashed using distilled water.

The unanodized, residual side of the aluminum substrate creates anelectorode that can act as either an anode or a cathode. An explainedbelow another material is placed on the other side of the PAMSEEmonolith to complete the battery system.

Another embodiment incorporates Anodized Aluminum Oxide protruding fromboth sides of an aluminum disk. If the AAO is created in this fashion,two other electrodes must be placed on the other sides of the PAMSEEmonolith. This alternate embodiment is described in detail below.

Membrane Example II Salt-Coated PAMSEE Monolith: Aluminum Electrode

IIA.—The pores in the AAO portion of the membrane/electrode monolith arecoated with organic salts, such as lithium triflate and lithium dodecylsulfonate, by the application of solutions of these salts in THF,followed by solvent evaporation at elevated temperatures in a nitrogenatmosphere. The PAMSEE monolith is heated by laying it flat on a heatingmantel. The application of the salt solutions is done drop wise on theAAO face of the PAMSEE monolith.

IIB.—The pores in the AAO portion of the membrane/electrode monolith arecoated with inorganic salts, such as lithium iodide and lithium bromide,by the direct application of these salts to the AAO face of the monolithand heating the monolith under nitrogen gas in a furnace to 400-500K orto the melting point of the salt. The monolith can be dried at 773 K inair and then coated with molten LiBr at the same temperature. The saltcoating activates the base membrane/electrode transforming it into aPAMSEE.

IIC.—The Fabrication of a AAO+LiI Solid-State Electrolyte/Separator

A circular area of 1.3 cm diameter is selectively anodized on one sideof a flat 2.5 cm×2.5 cm×0.0254 cm-thick piece of high purity (99.999%)aluminum metal using a single-sided anodizer system. The anodizer systemconsists of an o-ring that is compressed onto the top side of thealuminum surface using a cylindrical container with two openings; oneopening fits over and compresses the o-ring, the other opening is usedto fill the container with electrolyte and to insert the positiveelectrode. The cylindrical container contained 20 ml of a 0.3 m oxalicacid heavy water solution. The bottom side of the aluminum metal isplaced on top of a semiconductor thermoelectric module (Peltier) cooler,which maintained the electrolyte solution at 3-5° C. The negativeelectrode is connected to the aluminum metal. A potential of 40 volts isapplied between the two electrodes for a period of about 3 days. Thealuminum metal substrate with a circular top section of porous anodizedaluminum oxide (AAO) is floated on a pool of 2 M HCl acid solutioncontaining dissolved CuCl₂; the aluminum metal was completely removed byoxidation after 20 minutes. The free-standing disk of porous AAO wasrinsed with water. The thickness of the disk should be about 8 μm,measured by optical microscopy. The AAO disk is then dried under astream of nitrogen gas.

Membrane Example III Polymer Electrolyte and Salt-Coated PAMSEEMonolith: Aluminum Electrode

The pores 3 and outer face 5 of the second side 2 of an AAO portion ofthe PAMSEE monolith (see FIG. 1A) is coated with a layer of a polymerelectrolyte to form a soft ion conducting interface between the outerface 5 and an electrode. The polymer electrolyte is composed of PEO andlithium triflate and has an oxygen to lithium ion ratio of 8:1, and ismade by a well-know procedure. The pore walls 3 can be coated by placingthe PAMSEE monolith on the surface of a hot plate and heating to 400 Kin a dry nitrogen gas atmosphere. The polymer electrolyte can be smearedonto the surface of the AAO portion of the PAMSEE monolith and allowedto permeate the pores for a period of 10 minutes. Any excess polymer onthe top (and bottom) face of the AAO portion of the PAMSEE monolith isremoved from the surface leaving a thin surface layer. Complete anduniform coating of the pores with polymer electrolyte requires severalminutes to several hours of heating; longer periods of heating may berequired for thicker membranes.

Membrane Example IV Polymer Electrolyte Laminate and Salt-Coated PAMSEEMonolith: Aluminum-Lithium Battery

An exemplary laminate membrane can be fabricated by the followingprocedure. The pores of the AAO portion of the PAMSEE monolith are driedin an open-air furnace at 773 K and then coated with molten LiBr at thesame temperature by placing anhydrous LiBr powder in contact with themembrane surface for 30 minutes.

The membrane is then cooled and transferred to a nitrogen atmosphere andheated on a hot plate to 400 K. A PEO/Li-triflate polymer electrolyte issmeared onto the surface of the AAO portion of the PAMSEE monolith andexcess electrolyte is scraped off using a knife edge. A piece of lithiumfoil (anode) is contacted to the top surface of the laminate AAO portionof the PAMSEE monolith and the integrated aluminum electrode (cathode)is in contact with the bottom. A potential is measured across the twoelectrodes. The potential indicates the transport of ions through thethinly-laminated top surface and the pores of the AAO portion of thePAMSEE monolith.

Voltage measurements for lithium-ion cells employing Al₂O₃separator/electrolytes (using the specified salts) include: 2.5V/lithium triflate; 1.3 V/lithium dodecyl sulfate; 0.5 V/LiBr. Theseresults and preliminary electrochemical discharge curves indicate thatlithium ions encounter an oxygen environment on the AAO walls thatcoordinates ions and allows ion movement.

Electrodes

A physiochemcially-active membrane separator/electrolyte-electrode(PAMSEE) (or laminated PAMSEE) monolith, as described above, is pairedwith suitable first electrode (and sometimes second electrode) andhermetically sealed to form a functional electrochemical cell orbattery. Unlike sensors, which are unsealed and inherently open systems,the present invention calls for the use of electrode(s) that cover andisolate the pores from environmental agents such as gases and liquids,thereby forming a hermetically sealed system. Operation of a closedbattery system of the present invention requires that macroscopicquantities of an electroactive species contained within one electrode betransported through the nano-pores of the PAMSEE monolith to the otherelectrode. Exposure of the electrodes or the nano-pores of the PAMSEEmonolith to environmental agents such as oxygen and water wouldirreversibly impede battery operation.

In battery applications, the separator/electrolyte-electrode membrane(PAMSEE monolith) is sealed. That is, the pore openings of the AAOportion of the PAMSEE monolith are covered and sealed by an electrodematerial that can take up and release macroscopic quantities ofelectroactive ions transported through the PAMSEE monolith pores. In apreferred embodiment, the AAO-based PAMSEE monolith and second electrodeare hermetically sealed. The hermetic seal create a closed batterysystem, impermeable to outside gases.

A salient distinction between sensors and batteries is the quantity ofcharge that is transported through the nanopores. The optimal sensordevice conducts a nano-scale level (nanoamps) or smaller current inresponse to an environmental agent such as a gas or liquid. The optimalbattery device of the present invention conducts a macro-scale level(milliamps) or larger current in the charge and discharge process ofbattery operation. Sensors deliver minute currents to provide a responseto the detection of trace quantities of a gas or liquid. Batteriesdeliver large currents to provide energy to a device such as a motor orcomputer to perform work. The key attribute of a sensor device with alinear response is very high sensitivity to the sensed analyte. Highsensitivity requires very low sense currents, a sever limitation for ahigh-power battery. Batteries that deliver very low currents providepower to a limited number of devices.

It is a requirement that the composition of molecular species on theinterior walls of the nano-pores in a sensor device changes dramaticallywhen the sensor device is exposed to a gas or liquid molecular species(analyte). The magnitude of the sense signal is proportional to thequantity of adsorbed molecular species on the interior walls of thenano-pores in a sensor device. The composition of the molecular specieson the interior walls of the nano-pores in a battery device of thepresent invention is essentially constant for the charge and dischargeprocess of the battery operation.

The first (first and second in certain alternate embodiments) electrodematerials are placed or deposited on the face(s) of the PAMSEE monolith.The electrodes can be made of a variety of materials known in the art,or the corresponding alkali or alkaline ion materials including but notlimited to: MoO₃, Cr₃O₅, V₂O₅, V₆O₁₃, LiV₃O₅, MnO₂, LiCoO₂, LiNiO₂,LiMn₂O₄, LiVO₂, LiCrO₂, WO₃, TiO₂, TiS₂, MoS₂, NiPS₃, TiSe₃, TiTe₂,MoS₂, MoSe₂, InSe; coke, graphite, aluminum, C₇CoCl₂, poly(acetylene),poly(pyrrole), poly(vinylferrocene), poly(aniline), poly(p-phenylene),poly(phenylene sulfide).

The electrode materials can be attached to the PAMSEE using a variety ofmethods well known in the art including but not limited to variousadhesives, mechanical attachments (i.e. coupling devices) or othermaterials or means. The electrode(s) may also be attached using methodsknown in the art including but not limited to melting the electrodematerials onto the faces of the AAO membrane. Alternatively theelectrode(s) can be deposited upon the PAMSEE using various techniquessuch as electrochemical deposition, electrophoretic deposition, andsolution casting.

The electrode materials should be selected to correspond with thematerials of the PAMSEE monolith so as to form a functionalelectrochemical cell system. The electrodes are preferably impermeableto gasses and liquids.

In an alternate embodiment one or more faces of the AAOseparator/electrolyte-electrode are covered with a laminate beforeattachment of the electrodes, in one such embodiment an ion-conductingpolymer is applied to the faces covering the pores of first and secondfaces of the AAO separator/electrolyte.

Exemplary Micro/Nano-battery Systems

FIG. 6 illustrates one embodiment of the invented battery system having:a MnO₂ cathode and an AAO-based membrane separator/electrolyte-aluminumelectrode monolith. The pores of the AAO portion of the PAMSEE monolithwere coated with KOH salt to create a PAMSEE monolith as described indetail above. The PAMSEE monolith acts as a separator, electrolyte, andelectrode therefore, an additional electrolyte is not required as taughtfor membranes by the prior art.

FIG. 7 illustrates another embodiment of the invented system comprising:a lithium (foil) anode, and a membrane separator/electrolyte-electrodemonolith. In this case the AAO pores are coated with a polymer (i.e.PEO) which includes a salt (i.e. Li⁺ ROSO₃ ⁻) such as lithium triflate.The AAO-polymer/salt PAMSEE monolith acts as a separator, electrolyte,and electrode, therefore an additional electrolyte is not required astaught for membranes by the prior art.

Alternate Embodiment Monolithic Double-Cell BatterySeparator/Electrolyte-Electrode

FIG. 8 illustrates the membrane of the alternate double-cell batteryembodiment, which is similar to that of the other embodiments exceptthat anodized metal oxide is grown on both faces of a metal instead ofjust on one side. The result is a membrane that has a first section, amiddle section, and a second section. The first and second AAO-basedmembrane sections act as separator/electrolyte monoliths. The middlesection is a dual electrode, providing an electrode for the first andsecond sections.

FIGS. 9A-9C illustrates an alternate double-cell battery embodiment ofthe invention. The illustrated embodiment generally comprises a dualmembrane separator/electrolyte-electrode monolith having a first section101, a second section 102, and a middle section 103 situated in betweenthe first and second sections; wherein the first 101 and second sections102 are porous anodized aluminum oxide and the middle section 103 isaluminum metal; wherein a series of uniform, physiochemically active andfunctionalized ion pores 104 capable of adjustable ionic interaction runthe width of the first section 101;

wherein a series of uniform, physiochemically active and functionalizedion pores 106 capable of adjustable ionic interaction run the width ofthe second section 102;

wherein both the first 101 and second sections 102 act as both anelectrolyte and a separator;

wherein the middle section 103 acts as a first electrode for both first101 and second section 102;

wherein the pore walls of the first section 101 and have a coating 105;

wherein the pore walls of the second section 102 have a coating 107;

attaching a second electrode 110 to the first section 101 of themonolithic membrane; attaching a third electrode 111 to the secondsection 102 of the monolithic membrane. The double-cell battery iscreated by first creating a double sided base membrane (FIG. 9A) whichis then modified by coating the membrane pore walls with a definedcoating creating a double sided PAMSEE (FIG. 9B). The double sidedPAMSEE is then transformed into a double-cell battery by the attachmentof two outer electrodes.Preparing Monolithic Double-Cell Battery Separator/Electrolyte-Electrode

Aluminum strips (6.0 cm×1.5 cm×0.15 mm) of 98% purity were immersed in0.3 molal oxalic acid maintained at 276 K and anodized at 40 VDC,forming top and bottom transparent monolithic surface membranes having ametal (or metal alloy) interior and porous metal oxide (or metal alloyoxide) faces. The films were washed with deionized water, dried at 383 Kfor 15 minutes in air, and cooled under dry nitrogen. Removal of watercoating the pore walls was accomplished by heating the membranes to 330K under vacuum for two hours, or heating the membranes to 700 K underdry nitrogen. The pores in the AAO portion of the PAMSEE monolith arecoated with organic salts, such as lithium triflate and lithium dodecylsulfonate, by the application of solutions of these salts in THF,followed by solvent evaporation at elevated temperatures in a nitrogenatmosphere. The PAMSEE monolith is heated by laying it flat on a heatingmantel. The application of the salt solutions is done drop wise on theAAO face of the PAMSEE monolith.

Alternatively, the pores in the AAO portion of the PAMSEE monolith arecoated with inorganic salts, such as lithium iodide and lithium bromide,by the direct application of these salts to the AAO face of the PAMSEEmonolith and heating the PAMSEE monolith under nitrogen gas in a furnaceto 400-500 K or to the melting point of the salt. The PAMSEE monolithcan be dried at 773 K in air and then coated with molten LiBr at thesame temperature. An electrode composed of MnO2 is attached to one sideof the double-cell PAMSEE monolith and a lithium electrode is attachedto the other side. Both electrodes provide impervious gas/liquidbarriers for the AAO-based membranes of the PAMSEE monolith.

Electrodes and Modification of Alternate Membrane

The electrodes of the alternate double-cell battery embodiment can beattached and/or deposited as described previously and may be of the sametype of materials as discussed in detail above. Modifying the pores ofthe membrane can also be modified as discussed above.

In the illustrated embodiment shown in FIG. 8, a Li anode is attachedand/or deposited on the open outer face of the first section of themembrane completing the first half of the double-cell battery where themiddle aluminum section acts as a cathode. A MnO₂ cathode is attachedand/or deposited to the open face of the second section completing thesecond half of the double-cell battery where the middle aluminum sectionacts as the anode.

In the illustrated embodiment a polymer coating is applied to the porewalls of the first section of the membrane and a KOH coating is appliedto the pore walls of the second section prior to the deposition and/orattachment of the electrodes. Although the illustrated embodiment showsa preferred embodiment the pore walls can be coated with a variety ofcoatings as discussed in detail above.

Having described the basic concept of the invention, it will be apparentto those skilled in the art that the foregoing detailed disclosure isintended to be presented by way of example only, and is not limiting.Various alterations, improvements, and modifications are intended to besuggested and are within the scope and spirit of the present invention.Additionally, the recited order of the elements or sequences, or the useof numbers, letters or other designations thereof, is not intended tolimit the claimed processes to any order except as may be specified inthe claims. All ranges disclosed herein also encompass any and allpossible sub-ranges and combinations of sub-ranges thereof. Any listedrange can be easily recognized as sufficiently describing and enablingthe same range being broken down into at least equal halves, thirds,quarters, fifths, tenths, etc. As a non-limiting example, each rangediscussed herein can be readily broken down into a lower third, middlethird and upper third, etc. As will also be understood by one skilled inthe art all language such as “up to,” “at least,” “greater than,” “lessthan,” and the like refer to ranges which can be subsequently brokendown into sub-ranges as discussed above. Accordingly, the invention islimited only by the following claims and equivalents thereto.

All publications and patent documents cited in this application areincorporated by reference in their entirety for all purposes to the sameextent as if each individual publication or patent document were soindividually denoted.

1. A specialized battery with a physicochemically active membraneseparator/electrolyte/electrode (PAMSEE) produced by a processcomprising: providing a membrane/electrode monolith having a first andsecond side, the first side being a metal and the second side being ananodized metal oxide, the membrane/electrode having a plurality of poresrunning the thickness of its second side terminating into its firstside, wherein the pores have an inner wall, and wherein the first andsecond sides each have an outer face; coating the inner pore walls witha defined pore coating, wherein the defined pore coating is selectedfrom the group consisting of: salts, anions, cations and combinationsthereof forming a PAMSEE, and further wherein the defined pore coatingon the inside pore walls of the monolith has a thickness of less thanabout half the pore diameter; a first outer electrode is attached ordeposited on the second side's face, wherein the first outer electrodeis positioned over and is in ionic communication with the pores of thesecond face of the monolith to form a first seal, wherein the pores havediameters ranging from about 2 nm to about 150 nm, wherein the firstside of the monolith acts as the second electrode, and wherein the firstouter electrode attached to the first side of the monolith seals-off thepores from the ambient environment, and further wherein the pores arenot otherwise filled.
 2. The battery of claim 1, wherein second side ofthe monolith is a metal-alloy oxide selected from the group consistingof: aluminum oxide, silicone oxide, titanium oxide, magnesium oxide,vanadium oxide, zirconium oxide, germanium oxide, tin oxide, galliumoxide, indium oxide, iron oxide, chromium oxide, molybdenum oxide,nickel oxide, copper oxide, zinc oxide and combinations thereof.
 3. Thebattery of claim 1, wherein the second side's face of the monolith ismade of anodized aluminum oxide (AAO).
 4. The battery of claim 1,wherein the first and second electrodes are impermeable to gas andliquid, creating a closed battery system.
 5. The battery of claim 1,wherein the second side's face of the monolith is coated with anion-conducting polymer laminate prior to attachment or deposition of theelectrode, wherein the laminate coating has a thickness between about 1nm and 10 μm, and further wherein the laminate coating does not enterthe membrane pores.
 6. The battery of claim 1, wherein at least aportion of the pores have a tortuosity equal to
 1. 7. The battery ofclaim 3, wherein the first outer electrode is constructed of materialsselected from the group consisting of: MoO₃, Cr₃O₃, V₂O₅, V₆O₁₃, LiV₃O₈,MnO₂, LiCoO₂, LiNiO₂, LiMn₂O₄, LiVO₂, LiCrO₂, WO₃, TiO₂, TiS₂, MoS₂,NiPS₃, TiSe₃, TiTe₂, MoS₂, MoSe₂, InSe.; coke, graphite, aluminum, CFn,(C₂F)n, C₇CoCl₂, poly(acetylene), poly(pyrrole), poly(vinylferrocene),poly(aniline), poly(p-phenylene), poly(phenylenesulfide) andcombinations thereof.
 8. The battery of claim 3, wherein the firstelectrode is lithium.
 9. The battery of claim 3, wherein the firstelectrode is MnO₂.
 10. The battery of claim 3, wherein the firstelectrode is lithium and the coating is a salt.
 11. The battery of claim3, wherein the first electrode is MnO₂ and the coating is anion-conducting polymer.
 12. The battery of claim 3, wherein the porecoating is selected from the group consisting of: salts, anions, cationsand combinations thereof.
 13. The battery of claim 3, wherein the porecoating consists of one or more salts.
 14. The battery of claim 3,wherein the pore coating consists of one or more anions or cations. 15.The battery of claim 3, wherein the pore coating is imparted by meltinga salt onto the inner walls of the pores, wherein the salt is selectedfrom the group consisting of: lithium iodide, lithium bromide, lithiumchloride, lithium fluoride, and combinations thereof.
 16. The battery ofclaim 3, wherein the pore coating is imparted by: washing the membranecomponent of the monolith with an aqueous or organic solution, thesolution containing a solvent and at least one ionic species; andevaporating the solvent.
 17. The battery of claim 3, wherein the porecoating is imparted by: washing the membrane component of the PAMSEEmonolith with an organic solution, the solution containing a solvent andat least one ionic species; and evaporating the solvent, and wherein theorganic solution contains at least one compound selected from the groupconsisting of: propylene carbonate, ethylene carbonate,gamma.-butyrolactone, 1,3-dioxolane, dimethoxyethane, dimethylcarbonate, methylethyl carbonate, diethyl carbonate, tetrahydrofuran,dimethyl sulfoxide, polyethylene glycol dimethyl ether, methanol,formamide, propylene carbonate, ethylene carbonate,.gamma.-butyrolactone, 1,3-dioxolane, dimethoxyethane, dimethylcarbonate, methylethyl carbonate, diethyl carbonate, tetrahydrofuran,dimethyl sulfoxide, polyethylene glycol dimethyl ether and combinationsthereof.
 18. The battery of claim 3, wherein the pore coating isimparted by: washing the pores of the monolith with an aqueous solution,the solution containing a solvent and at least one ionic species; andevaporating the solvent, and wherein the aqueous solution is selectedfrom the group consisting of: sodium hydroxide, potassium hydroxide,ammonium hydroxide, lithium hydroxide, cesium hydroxide aluminumchloride, aluminum chloride hexahydrate, sodium chloride, potassiumchloride, cesium chloride, aluminum nitrate, aluminum sulphate, aluminumchromate, ammonium chromate, sodium chromate, potassium chromate, ZnCl,AlCl₃, AlCl₃-6H₂O, Al(NO₃)₃, HCl, NH₄OH, H₂SO₄, NaOH, KOH, LiOH, CsOH,NaCl, KCl, CsCl, Al₂(SO₄)₃ and combinations thereof.
 19. The battery ofclaim 3, wherein the pore coating is a metal oxide and wherein the metaloxide is deposited by a process selected from the group consisting of:atomic layer deposition (ALD), chemical vapor deposition (CVD), chemicalreaction with a gas, chemical reaction with a solution reagent, andcombinations thereof.
 20. The battery of claim 3, wherein the porecoating is an ion-conducting polymer.
 21. The battery of claim 3,wherein the pore coating is an ion-conducting polymer, and wherein theion conducting polymer contains at least one salt selected from thegroup consisting of: lithium perchlorate (LiClO.sub.4), lithiumtetrafluoroborate (LiBF.sub.4), lithium hexafluorophosphate(LiPF.sub.6), lithium trifluoromethanesulfonate (LiCF.sub.3SO.sub.3),lithium bistrifluoromethanesulfonyl amide (LiN(CF.sub.3SO.sub.2).sub.2),and lithium triflate.
 22. The battery of claim 3, wherein the porecoating is an ion conducting polymer selected from the group consistingof: polyether, polyethylene oxide, polypropylene oxide,polyacrylonitrile, polyvinylidene fluoride, polyvinylidene chloride,polymethyl methacrylate, polymethyl acrylate, polyvinyl alcohol,polymethacrylonitrile, polyvinyl acetate, polyvinylpyrrolidone,polyethyleneimine, polybutadiene, polystyrene, polyisoprene, vinylidenefluoridehexafluoropropylene coploymer, poly(ethylene oxide),poly(propylene oxide), polyethylene glycols, polypropylene glycols,propylene carbonate, ethylene carbonate, dioctyl sebacate, diethylphthalate, derivatives of these polymers and combinations thereof.